249 research outputs found

    Effects of Cationic Ammonium Gemini Surfactant on Micellization of PEO–PPO–PEO Triblock Copolymers in Aqueous Solution

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    Effects of cationic ammonium gemini surfactant hexamethylene-1,6-bis­(dodecyldimethylammonium bromide) (12–6–12) on the micellization of two triblock copolymers of poly­(ethylene oxide)–poly­(propylene oxide)–poly­(ethylene oxide), F127 (EO<sub>97</sub>PO<sub>69</sub>EO<sub>97</sub>) and P123 (EO<sub>20</sub>PO<sub>70</sub>EO<sub>20</sub>), have been studied in aqueous solution by differential scanning calorimetry (DSC), dynamic light scattering (DLS), isothermal titration calorimetry (ITC), and NMR techniques. Compared with traditional single-chain ionic surfactants, 12–6–12 has a stronger ability of lowering the CMT of the copolymers, which should be attributed to the stronger aggregation ability and lower critical micelle concentration of 12–6–12. The critical micelle temperature (CMT) of the two copolymers decreases as the 12–6–12 concentration increases and the ability of 12–6–12 in lowering the CMT of F127 is slightly stronger than that of P123. Moreover, a combination of ITC and DLS has shown that 12–6–12 binds to the copolymers at the temperatures from 16 to 40 °C. At the temperatures below the CMT of the copolymers, 12–6–12 micelles bind on single copolymer chains and induce the copolymers to initiate aggregation at very low 12–6–12 concentration. At the temperatures above the CMT of the copolymers, the interaction of 12–6–12 with both monomeric and micellar copolymers leads to the formation of the mixed copolymer/12–6–12 micelles, then the mixed micelles break into smaller mixed micelles, and finally free 12–6–12 micelles form with the increase of the 12–6–12 concentration

    CO Oxidation over AuPd(100) from Ultrahigh Vacuum to Near-Atmospheric Pressures: The Critical Role of Contiguous Pd Atoms

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    CO Oxidation over AuPd(100) from Ultrahigh Vacuum to Near-Atmospheric Pressures: The Critical Role of Contiguous Pd Atom

    Modulation of Fibrillogenesis of Amyloid β(1−40) Peptide with Cationic Gemini Surfactant

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    Modulation of the fibrillogenesis of amyloid peptide Aβ(1−40) with the cationic gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (C12C6C12Br2) has been studied. Both UV−vis and AFM results show that C12C6C12Br2 monomers can promote the fibrillogenesis of Aβ(1−40) while its micelles inhibit this process. The electrostatic/hydrophobic force balance plays important roles in determining the Aβ(1−40) aggregation style and the secondary structures. When the surfactant positive charges are close to the Aβ(1−40) negative charges in number, the hydrophobic interaction is highly enhanced in the system. Both the nucleation rate and the lateral association between fibrils are greatly promoted. However, when the surfactant positive charges are in excess of the Aβ(1−40) negative charges, the electrostatic interaction is strengthened. In this case, the lateral association is inhibited and the α-helix to β-sheet transition in the secondary structure is prevented. Simultaneously, another assembly pathway is induced to give the amorphous aggregates. Moreover, the size and surface roughness of the Aβ(1−40) aggregates also vary upon increasing C12C6C12Br2 concentration

    Formation and Decomposition of C<sub>3</sub> Metallacycles from Ethylene and Methylene on MoAl Alloy Thin Films

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    The reaction between adsorbed ethylene and methylene species has been investigated on a molybdenum−aluminum alloy grown from Mo(CO)6 on a planar alumina film formed on a Mo(100) single crystal in ultrahigh vacuum. Di-σ-bonded ethylene reacts with carbene species, formed on the surface from methylene iodide, to form a C3 metallacycle. This predominantly decomposes to yield propylene, while a smaller portion yields cross-metathesis products since 12C13CH4 is formed from reaction between 13C2H4 and 12CH2. This work demonstrates for the first time that the reaction proceeds in heterogeneous phase via a C3 metallacycle as proposed in the Hérisson-Chauvin mechanism

    Temperature-Induced Aggregate Transitions in Mixtures of Cationic Ammonium Gemini Surfactant with Anionic Glutamic Acid Surfactant in Aqueous Solution

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    The aggregation behaviors of the mixtures of cationic gemini surfactant 1,4-bis­(dodecyl-<i>N</i>,<i>N</i>-dimethyl­ammonium bromide)-2,3-butanediol (C<sub>12</sub>C<sub>4</sub>(OH)<sub>2</sub>C<sub>12</sub>Br<sub>2</sub>) and anionic amino acid surfactant <i>N</i>-dodecanoyl­glutamic acid (C<sub>12</sub>Glu) in aqueous solution of pH = 10.0 have been studied. The mixture forms spherical micelles, vesicles, and wormlike micelles at 25 °C by changing mixing ratios and/or total surfactant concentration. Then these aggregates undergo a series of transitions upon increasing the temperature. Smaller spherical micelles transfer into larger vesicles, vesicles transfer into solid spherical aggregates and then into larger irregular aggregates, and entangled wormlike micelles transfer into branched wormlike micelles. Moreover, the larger irregular aggregates and branched micelles finally lead to precipitation and clouding phenomenon, respectively. All these transitions are thermally reversible, and the transition temperatures can be tuned by varying the mixing ratios and/or total concentration. These temperature-dependent aggregate transitions can be elucidated on the basis of the temperature-induced variations in the dehydration, electrostatic interaction, and hydrogen bonds of the headgroup area and in the hydrophobic interaction between the hydrocarbon chains. The results suggest that the surfactants carrying multiple binding sites will greatly improve the regulation ability and temperature sensitivity

    Aggregation Behavior of Nitrophenoxy-Tailed Quaternary Ammonium Surfactants

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    Cationic surfactants N,N,N-trimethyl-10-(4-nitrophenoxy)decylammonium bromide (N10TAB) and N,N,N‘,N‘-tetramethyl-N,N‘-bis[10-(4-nitrophenoxy)decyl]-1,6-hexanediammonium dibromide (N10-6-10N), bearing aromatic nitrophenoxy groups in the ends of their hydrophobic chains, have been synthesized, and their self-assembling properties in aqueous solutions have been studied by conductivity, isothermal titration microcalorimetry, 1H NMR spectroscopy, and dynamic light scattering. Below the critical micelle concentration, N10-6-10N can form premicelles with 2 or 3 surfactant molecules. Beyond the critical micelle concentration, the two surfactants have strong self-aggregation ability and can form micelles of rather small size and with small aggregation numbers N, which are 30 ± 3 for N10TAB and 20 ± 2 for N10-6-10N, respectively. Also, the variations in 1H NMR signals at different surfactant concentrations provide the information on the environmental change of the surfactants upon their micellization progress. The most prominent phenomenon is the shielding effect of the aromatic groups over the protons in the aliphatic chains, implying that the nitrophenoxy groups partially insert into the micelles and face the several middle methylenes of the hydrophobic side chains
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